Process of extracting sulfur from the sulfur-containing constituents of petroleum.



, PATENTED JAN. 2, 1906. H. S. BLAGKMORB. PROCESS OF BX'TRAGTING SULFURFROM THE SULFUR CONTAINING GONSTITUENTS 0F PETROLEUM.

APPLICATION FILED DBO. 12. 1904 Witvwmu UNITED STATES PATENT OFFIOE.

HENRY SPENCER BLAOKMORE, OF MOUNT VERNON, NEW YORK, ASSIGNOR, BY DIRECTAND MESNE ASSIGNMENTS, TO BLACK-FORD UTILITY OIL COMPANY, A CORPORATIONOF THE DISTRICT OF COLUMBIA.

PROCESS OF EXTRACTING SULFUR FROM THE SULFUR-CONTAINING CO NSTITUENTS 0FPETROLEUM.

Specification of Letters Patent.

Patented Jan. 2, 1906.

Application filed December 12,1904. Serial No. 236,420.

T0 on whom it may concern:

Be it known that I, HENRY SPENCER BLACK- MORE, acitizen of the UnitedStates, residing at Mount Vernon, in the county of Westchester and Stateof New York, have invented certain new and useful Improvements inProcesses of Extracting Sulfur from the Sulfur-Containing Constituentsof Petroleum, of which the following is a specification.

The object of my invention is to separate sulfur from sulfur-containingpetroleums and similar compounds or constituents thereof and producehydrogen carbid by the direct formation of insoluble sulfur compoundsand precipitation thereof from the liquid or fluid oils or substances orother constituents in such a manner as to facilitate the purificationand effect a saving in' time and labor as compared with processes forthe direct absorption of sulfur from the liquid or fluid petroleumscontaining sulfur employed hitherto; and it consists in exposing thesulfur containing petroleum to theaction of a double carbid of hydrogenand a metal, such as a carbid of hydrogen and zinc, preferably thatcompound commonly known as zinc-methid or zinc-methyl, (C2H0ZI1 orZnH6C2,) which compounds are commonly referred to in chemistry under thename of metallo-organic compounds, whereby the sulfur of thesulfurcontaining petroleum or constituent thereof unites with the zinccontent of the double carbid, with the liberation of the hydrogen carbidI with which it is associated, whichhydrogen carbid unites with thepetroleum from which the sulfur has been separated.

In carrying out my invention I take a quantity of sulfur-containingpetroleum and gradually add thereto a double carbid of zinc andhydrogen,commonly known as zinc-methyl, care being taken to introducethe zinc-hydrogen carbid below the surface of the oil out of contactwith the air by supplying the same from an elevated reservoir or otherconvenient means and thoroughly agitating the same with the sulfurcontaining petroleum, the zinc hydrogen carbid being introduced in aboutequivalent proportions to precipitate on methyl sulfida hydrocarboncompound containing sulfur, analogous in character to thesulfur-containing petroleum:

When methyl sulfid (C2H6S) is dissolved in an oil, such as petroleum,and exposed to the action of zinc-hydrogen carbid, (ZnHtOz), the sulfurof the methyl sulfid combines with zinc and is precipitated as zincsulfid, while the carbon and hydrogen combine to produce ethane.

While the employment of the double carbid of zinc and hydrogen as aprecipitant of sulfur from sulfur-containing oils would seem to be anexpensive operation, it should be noted that the sulfur content ofsulfurcontaining pe troleums rarely exceeds six-tenths of one per cent.

The manner in which I prefer to carry out my process may be readilyunderstood by referring to the accompanying drawings, in which Figure 1represents a front view or elevation of a series of communicatingvessels in which the oil is purified provided with receptacles forsupplying or conveying oil and purifying agent thereto and aprecipitating or settling tank for receiving and separating the purifiedmaterial. Fig. 2 is a transverse verthial section of one of theoil-purifying vesse s.

On the drawings the numeral 1 designates a receptacle in which the oilis purified provided withthe jacket 2 for containing a fluid for thepurpose of abstracting heat from the reacting ingredients within theapparatus and cooling the same in cases where heat is evolved and a coil3, provided with an inlet 4 and outlet 5, controlled by the valves 6 and7 for the purpose of heating the reacting ingredients by passing steamtherethrough in cases where heavier petroleum products are purified orsubstituting a current of water through the coil in place of steam whenheat is spontaneously evolved. The vessel is also provided with a cover8, having an outlet 9, controlled by the Valve 10, and through whichcover pass the feeding-pipes 11 and 12, the latter of which is locatedWithin the former and both of which terminate within and near the bottomof the vessel. The pipe 12 passes directly through a reducer orstufling-box (not shown) in the T 13, while the pipe 11 communicatesdirectly with the T 13 through the inlet-pipe 1 L, controlled by valve15, the pipe 12 being also controlled by a valve 16. The pipe 11 passesinto the vessel through a stuffing-box 17 in the cover thereof.

The vessel 1 is provided at its lower end with an outlet .18,cont-rolled by a valve 19, for the purpose of discharging any impuritieswhich may separate from the oil and precipitate in the apparatus, andalso interiorly with a perforated disk 42 for the purpose of supportinga mass of separators or mixers, such as glass marbles, inert to thereacting ingredients and employed for the purpose of causing theingredients to become thoroughly mixed in their passage up through theinterstices between the same. The mixing of the ingredients supplied tothe vessel through the inlet-pipes 11 and 12 is also facilitated bypassing an inert gas, such as carbonic-acid gas, into and up through thevessel by means of the pipe 20, controlled by valve 21, which gas mayescape through the outlet-pipe 9 upon opening the valve 10. The jacket 2is provided with an inlet-pipe 22, controlled by valve 23, andoutlet-pipe 24, controlled by Valve 25. The object of having valves atboth inlet and outlet of the various parts of the apparatus is for thepurpose of regulating and controlling fluids which may pass therethroughin either direction, as the exigency of the case may require, be iteither steam for heating or water for cooling. The ingredients conveyedinto the vessel through the inlet-pipes 11 and 12 after becomingthoroughly mixed after passing up through the interstices between thesmall glass marbles contained in the vessels and reacting upon eachother overflow through the pipe 26, controlled by the valve 27 carryingwith them in suspension any solid precipitate in afinely-divid ed statewhich may have been produced, the same being retained in suspendedcondition by the assistance of the ebullition of the inert gas, such ascarbon dioxid, passed through the vessel, the purified ingredientsholding in suspension the solid products of the reaction being conveyedto a precipitating and separating tank 28, Fig. 1, whichprecipitating-tank is provided with a gas-outlet 29, controlled by aninward check-valve 30, and also an outlet 31, controlled by a valve 32for drawing off the purified oil after the solid suspended matter hassettled to the bottom of the tank. This settling or precipitating tankis also provided with manholes 33 and 34 for the purpose of removing theprecipitate and cleaning the tank.

In carrying on my process for the purification of sulfurous petroleumwith the employment of zinc-hydrogen carbid as a precipitant for thesulfur content I place the sulfur-containing petroleum in the reservoir35, Fig. 1,

provided with a liquid-gage 36 and an outlet 37, controlled by the valve15. I also introduce into the reservoir 38, which preferably contains aportion of some light purified petroleum product, such as benzin, zinchydrogen carbid, (zinc-methyl,) the said receptacle being provided withthe liquid-gage 39 and outlet-pipe 40, controlled by valve 41. Beforeintroducing the sulfurous petroleum and zinc-hydrogen carbid into thepurifying apparatus care must be taken to displace all the air from thesame by passing into and through the apparatus and communicating pipesan inert gas, such as carbonic-acid gas, which is introduced through thepipe 20, controlled by the valve 21. This prevents the loss ofzinc-hydrogen carbid (Zinc-methyl) by spontaneous oxidation.

The air having been discharged from the apparatus, a current of carbondioxid is continuously passed through the vessel 1 and graduallydischarged through the pipe 9, controlled by the valve 10. The sulfurouspetroleum is then admitted to the vessel by opening valve 15, therebypassing through pipes 14: and 11 into the vessel 1. As soonas vessel 1is partly filled with sulfurous oil zinchydrogen carbid (Zinc-methyl) isgradually conveyed into the vessel through pipe 12 by opening valves 41and 16 to vessels A, B, and C, respectively, as the sulfurous petroleumreaches the different vessels through the overflow-pipe 26, the valve 27being open. As the zinc-hydrogen carbid enters the sulfurcontainingpetroleum it reacts therewith, precipitating the sulfur in the form ofzinc sulfid and generating hydrocarbon, which assimilates and mixes withthe purified petroleum, the zinc sulfid being held in suspension in thepetroleum by the agitation caused by the passage up through the same ofthe inert carbon dioxid introduced through pipe 20 and passes on throughthe vessels A, B, and G and into the precipitating-tank 28, where theZinc sulfid is allowed to settle. When the apparatus has becomesufiiciently filled with petroleum supplied from the reservoir 35, whichis kept filled as the oil is gradually discharged therefrom, theZinc-hydrogen carbid (Zinc-methyl) is carefully fed into the vessels A,B, and (J directly by opening the valves 16, so that by the time thepetroleum has passed through the series of vessels and out into theprecipitating or settling tank, together with its suspended zinc sulfid,the zinc-hydrogen carbid (zincmethyl) will have been supplied to thesulfurous petroleum in proportion of approximately three pounds perpound of sulfur contained in the sulfurous petroleum. Any excess ofzinc-methyl sulfid retained in the oil after purification may be readilyremoved by passing a current of air through the same, which oxidizes thezinc-methyl carbid, producing zinc oxid. During the passage of the IIOsulfurous petroleum through the vessel 1, together with thezinc-hydrogen carbid (zincmethyl) the mixture may be heated by passingsteam through the coil 3 to facilitate reaction, or in cases where thelighter sulfurcontaining petroleums are employed, which react more orless spontaneously and generate more or less' heat, the heat may beabstracted by passing a current of water through the coil instead ofsteam. The jacket 2, ordinarily used for the purpose of cooling thereacting ingredients, may also be employed asa steamjacket in caseswhere the heavier sulfur-containing petroleum products are beingpurified and the application of heat is necessary to facilitate thepurifying action.

Any zinc sulfid or other precipitate which may accumulate at the lowerpart of the apparatus below the perforated disk 42, employed forsupporting the marbles or other mixing devices, may be removed from timeto time by opening the valve 19 and withdrawing a portion of thepetroleum, together with the precipitate, and again closing the same asthe process proceeds.

I do not desire to confine myself to the employment of the double carbidof zinc and hydrogen, but reserve the right to use other metal-hydrogencarbids or so-called metalloorganic compounds as a precipitant forsulfur from sulfur-containing petroleums without departing from thespirit of my invention, which consists in employing, in combination withhydrogen and carbon, a metal having such superior afiinity for sulfurthat it will abstract the same from the petroleums with which it isassociated. Some of the other compounds may be noted, asmercury-hydrogen carbid, tin-hydrogen carbid, lead-hydrogen carbid,antimony-hydrogen carbid, 850. These metal-hydrogen carbids being ofendothermic nature evolve considerable heat upon decomposition andnaturally heat the oils when employed to precipitate the sulfur therein,and it is advisable in some cases to refrigerate the petroleums duringthe process of treatment. These double carbids are also quite unstable,and many of them are spontaneously combustible. It is thereforenecessary to retain the same in closed containers and supply thesubstance to the sulfur-containing oil below the surface thereof,thoroughly agitating the same therewith in order to bring the compoundwithin reacting communication without exposure to the atmosphere. One ofthe principal objects in employing the metal-hydrogen carbids asprecipitants for sulfur from sulfur-containing petroleums is that themetal thus combined as double carbid readily mixes with or dissolves inthe oil, whereby the metal content thereof is brought into closeassociation with the petroleum. I can use or employ any availablesulfur-containing hydrocarbon or sulfurous petroleum, and I can employ,as aforesaid, any metal-hydrogen carbid in place of the zinc-hydrogencarbid so long as the sulfur of the sulfur-containing hydrocarbon orsulfurous petroleum has such superior affinity for the metal content ofthe metal-hydrogen carbid that it is withdrawn or separated therefromwhen brought in contact therewith, producing an insoluble metal sulfidwhich may be readily separated from the oil by allowing it to settle orprecipitate and removing the petroleum by decantation, filtration, orother convenient means. I also do not desire to confine myself to thepurification of petroleum as a composite composition, but reserve theright to purify any individual product of the sulfur-containingpetroleum which may be or may have been separated into its individualproducts by fractional distillation or otherwise prior to separating thesulfur therefrom, whereby the individual ingredients of the petroleummay be purified separately instead of collectively, as is the case wherethe petroleum is exposed to the action of a metal-hydrogen carbiddirect, and purified by the abstraction of sulfur before separation ofthe individual ingredients.

The term metal-hydrogen carbid employed in the specification and claimshas reference to compounds consisting of carbon and hydrogen with ametal, such as is commonly known as the metallo-organic compounds ofmetal substitution products of hydrocarbon. These fluid compounds,either gaseous or liquid, readily dissolve in and assimilate with thehydrocarbons, such as petroleum, and are easily decomposed by anysulfurous contamination with the precipitation of the metal from themetal-hydrogen carbid as a sulfid, while the purified hydrocarbon orpetroleum is augmented in value by the hydrogen carbid or hydrocarbonproduced as the metal is precipitated, which readily unites with thepetroleum, increasing the hydrogen and carbon constituents thereof.

By the term sulfur-containing petroleum as employed in thisspecification and claims I intend to include petroleum containing sulfurunder any or all conditions, either free, combined as a substitutionproduct in hydrocarbons, or other compounds containing sulfur dissolvedin or assimilated with petroleum or its constituents or sulfurcontaining oil, whereby the oil, petroleum, or constituent thereofisrendered sulfurous in accordance with the general understanding of theterm.

Having now described my invention, what I claim as new, and desire tosecure by Letters Patent,-is

1. The process of removing sulfur from pctroleum containing the same,which consists in exposing sulfur-containing petroleum to the action ofa metal-hydrogen carbid.

2. The process of removing sulfur from pe- IIO troleum containing thesame, which consists in exposing the sulfur-containing petroleum to theaction of zinc-hydrogen carbid.

3. The process of removing sulfur from the constituents of petroleum,which consists in exposing the sulfur-containing constituent to theaction of a metal-hydrogen carbid.

4. The process of removing sulfur from the constituents of petroleum,which consists in exposing the sulfur-containing constituent to theaction of zinc-hydrogen carbid.

5. The process of removing sulfur from oil containing the same, whichconsists in exposing the sulfur-containing oil to the action of ametal-hydrogen carbid.

6. The process of removing sulfur from oil containing the same, whichconsists in exposing the sulfur-containing oil to the action ofzinc-hydrogen carbid.

7. The process of producing hydrogen carbid, which consists in exposinga metal-hydrogen carhid to the action of sulfurous petroleum maintainedat a reacting temperature.

8. The process of producing hydrogen carbid, which consists in exposingzinc-hydrogen carbid to the action of sulfurous petroleum maintained ata reacting temperature.

9. The process of producing hydrogen carbid, which consists in mixingsulfurous petroleum with a metal-hydrogen carbid while alostracting theheat evolved, by refrigeration.

10. The process of removing sulfur from sulfurous petroleum, whichconsists in exposing it to the action of a metal-hydrogen carloidmaintained at a reacting temperature.

11. The process of purifying petroleum, which consists in exposingpetroleum to the action of a metal-hydrogen carbid.

12. The process of purifying petroleum, which consists in exposing arefrigerated petroleum to the action of a metal-hydrogen carhid.

In testimonywhereof I affix my signature in presence of two witnesses.

HENRY SPENCER BLAGKMORE.

Witnesses:

G. C. l/VRIGHT, H. N. JENKINS.

